WO2013018454A1 - 被めっき層形成用組成物、および金属層を有する積層体の製造方法 - Google Patents

被めっき層形成用組成物、および金属層を有する積層体の製造方法 Download PDF

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WO2013018454A1
WO2013018454A1 PCT/JP2012/065849 JP2012065849W WO2013018454A1 WO 2013018454 A1 WO2013018454 A1 WO 2013018454A1 JP 2012065849 W JP2012065849 W JP 2012065849W WO 2013018454 A1 WO2013018454 A1 WO 2013018454A1
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group
layer
plated
plating
polymer
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PCT/JP2012/065849
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English (en)
French (fr)
Japanese (ja)
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季彦 松村
加納　丈嘉
裕久 外園
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富士フイルム株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • C25D5/56—Electroplating of non-metallic surfaces of plastics
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1689—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1813—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by radiant energy
    • C23C18/1817—Heat
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1813—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by radiant energy
    • C23C18/182—Radiation, e.g. UV, laser
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1837—Multistep pretreatment
    • C23C18/1844—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1862—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by radiant energy
    • C23C18/1865—Heat
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1862—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by radiant energy
    • C23C18/1868—Radiation, e.g. UV, laser
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1886—Multistep pretreatment
    • C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2026—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by radiant energy
    • C23C18/2033—Heat
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2026—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by radiant energy
    • C23C18/204—Radiation, e.g. UV, laser
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C—CHEMISTRY; METALLURGY
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    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/48—Coating with alloys
    • C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper

Definitions

  • the present invention relates to a composition for forming a layer to be plated, a method for producing a laminate having a metal layer using the composition, and a novel polymer useful for the composition.
  • a metal wiring board in which wiring with a metal pattern is formed on the surface of an insulating substrate has been widely used for electronic components and semiconductor elements.
  • "subtractive method” is used as a method for producing such a metal wiring board.
  • a photosensitive layer that is exposed to actinic rays is provided on a metal layer formed on the surface of the substrate, this photosensitive layer is subjected to pattern exposure, and then developed to form a resist image, In this method, the metal layer is etched to form a metal pattern, and finally the resist is removed.
  • the adhesion between the substrate and the metal layer is expressed by the anchor effect generated by providing irregularities on the substrate surface. For this reason, when the obtained metal pattern is used as a metal wiring, there is a problem that high frequency characteristics are deteriorated due to the unevenness of the substrate interface portion of the metal pattern.
  • a strong acid such as chromic acid
  • Patent Document 1 discloses that a polymer layer (layer to be plated) having a crosslinkable group and an interactive group is formed on a substrate, and the layer to be plated is treated with an alkaline aqueous solution. Then, a method for plating the layer to be plated is disclosed. According to Patent Document 1, the method can form a metal layer having excellent adhesion between the substrate and the metal layer and having high uniformity of plating without roughening the surface of the substrate. It is disclosed that it can be done.
  • the plating solution used in the plating process is continuously used for a plurality of layers to be plated. Therefore, when using the plating solution, it is important that the solution stability is maintained for a long time without being contaminated.
  • the plating method described in Patent Document 1 was carried out and the liquid stability of the plating solution used at that time was examined, insoluble matter was generated in the plating solution, and the liquid stability was It was not always enough.
  • the present inventors have further studied the above-mentioned problems, and the polymer component in the layer to be plated is decomposed and eluted during the alkaline aqueous solution treatment of the layer to be plated. It was found that the liquid stability of the liquid was lowered.
  • the present invention has a layer to be plated that has sufficient resistance to an alkaline aqueous solution and that can form a layer to be plated in which plating unevenness and plating solution contamination are suppressed during plating.
  • An object is to provide a forming composition.
  • Another object of the present invention is to provide a method for producing a laminate having a metal layer with excellent adhesion, in which generation of plating unevenness and contamination of the plating solution are suppressed, using the composition for forming a layer to be plated.
  • the present inventors have improved the resistance to an aqueous alkali solution by using a polymer having a functional group capable of converting hydrophilicity and hydrophobicity and a crosslinkable group having a high resistance to an aqueous alkali solution.
  • the inventors have found that the affinity for the plating catalyst can be ensured, and have completed the present invention.
  • composition for forming a layer to be plated according to (1) wherein the functional group is a functional group that generates carboxylic acid, sulfonic acid, or sulfinic acid when heated, supplied with acid, or irradiated with radiation.
  • the functional group has a group represented by any one of the following general formulas (1) to (4).
  • (4) The composition for forming a layer to be plated according to any one of (1) to (3), further comprising a crosslinking agent.
  • the manufacturing method of the laminated body which has a metal layer as described in said (6) further equipped with the process (H) which etches the said metal layer in a pattern shape, and forms a patterned metal layer.
  • a wiring board comprising the laminate according to (8).
  • the composition for to-be-plated layer formation which has sufficient tolerance with respect to alkaline aqueous solution, and can form the to-be-plated layer which suppresses generation
  • the manufacturing method of the laminated body which has generation
  • FIGS. 3A to 3D are schematic cross-sectional views sequentially showing each manufacturing process in the first embodiment of the method for manufacturing a laminated board of the present invention.
  • (A) to (E) are schematic cross-sectional views sequentially showing each manufacturing process in the second embodiment of the method for manufacturing a laminate of the present invention.
  • the composition for forming a layer to be plated is a specific functional group (hereinafter also referred to as a polar conversion group) that changes from hydrophobic to hydrophilic by heat, acid or radiation, and a highly resistant to alkaline aqueous solution. It is characterized in that it contains a polymer having a crosslinkable group (hereinafter, also simply referred to as a specific crosslinkable group). Moreover, the manufacturing method of the laminated body which has a metal layer has the characteristics in the point which provided the process of converting the polarity of this functional group after making it contact with alkaline aqueous solution.
  • a conventionally known layer to be plated cannot be said to have sufficient resistance to an aqueous alkali solution, and part or most of the polymer in the layer to be plated is decomposed and eluted when brought into contact with the aqueous alkali solution.
  • the layer to be plated has a low affinity for a plating catalyst solution or a plating solution and has sufficient adhesion. Can't get a layer.
  • a specific crosslinkable group having high resistance to an aqueous alkali solution is introduced, and when the contact with the aqueous alkali solution is performed, the polarity of the polarity converting group in the layer to be plated is made hydrophobic.
  • the hydrophobicity of the layer to be plated is increased, and resistance to an alkaline aqueous solution is imparted.
  • the polarity of the polarity conversion group is changed from hydrophobic to hydrophilic by a predetermined treatment, and the layer to be plated is made more hydrophilic, and the affinity for subsequent plating catalyst solution and plating solution is increased. Increase.
  • a laminate having a metal layer with little plating unevenness can be obtained while suppressing contamination of the plating solution.
  • the composition for forming a layer to be plated contains a polymer having a polarity converting group and a specific crosslinkable group.
  • the layer to be plated formed from the composition changes the hydrophilicity / hydrophobicity of the polarity conversion group from hydrophobic to hydrophilic by heating, supply of acid, or irradiation of radiation, and as a result, the layer to be plated
  • the hydrophilicity / hydrophobicity of the layer also changes from hydrophilic to hydrophobic. That is, the layer to be plated is a wettability changing layer in which the contact angle with water is reduced by heating, acid supply, or irradiation with radiation.
  • the polymer has a polarity converting group and a specific crosslinkable group. First, the polar conversion group will be described in detail, and then the crosslinkable group will be described in detail.
  • the polarity converting group is a functional group that changes from hydrophobic to hydrophilic by heat, acid, or radiation.
  • a known functional group can be used.
  • a carboxylic acid group or sulfone can be obtained by heating, supplying acid, or irradiating with radiation. It is preferably a functional group that generates an acid group or a sulfinic acid group, more preferably a functional group that generates a carboxylic acid group or a sulfonic acid group, and a carboxylic acid group that is superior in adhesion of the metal layer. More preferably, the resulting functional group.
  • the polar conversion group includes (A) a functional group that changes from hydrophobic to hydrophilic by heat or acid (hereinafter also referred to as polar conversion group A), and (B) from hydrophobic to hydrophilic by radiation (light). Examples thereof include functional groups that change (hereinafter, also referred to as polarity conversion groups B), which will be described in detail below.
  • Polarity converting group A examples include known functional groups described in literatures. For example, alkylsulfonic acid ester groups, disulfone groups, sulfonimide groups (described in JP-A-10-282672), alkoxyalkyl ester groups (described in EP0652483, WO92 / 9934), t-butyl ester groups, and other silyl esters And carboxylic acid ester groups protected by acid-decomposable groups described in the literature such as vinyl groups and the like (described in H. Ito et al., Macromolecules, vol. 21, pp. 1477).
  • Masahiro Tsunooka “Surface” vol. 133 (1995), p. 374, iminosulfonate group described by Masahiro Tsunooka, Polymer preprints, Japan vol. 46 (1997), p.
  • Examples thereof also include ⁇ ketone sulfonate esters described in 2045, nitrobenzyl sulfonate compounds described in JP-A-63-257750, and functional groups described in JP-A-2001-117223.
  • a group represented by the general formula (1) for example, a tertiary carboxylic acid ester group
  • a group represented by the general formula (2) for example, aryl
  • an alkyl ester group a group represented by the general formula (3) (for example, an alkoxyalkyl ester group), or a group represented by the general formula (4) (for example, a secondary alkyl sulfonate group). It is done.
  • the group represented by General formula (1) or General formula (2) is more preferable at the point which plating unevenness is suppressed more and adhesion with a metal layer is more excellent, and it represents with General formula (1). More preferred are groups. Below, each group is explained in full detail.
  • Preferred embodiments of the polar conversion group A include an embodiment having a group represented by the following general formula (1). * Indicates a binding position.
  • R 1 , R 2 , and R 3 each independently represent an alkyl group that may have a substituent or an aryl group that may have a substituent.
  • the number of carbon atoms in the alkyl group is preferably from 1 to 22 carbon atoms, more preferably from 1 to 8 carbon atoms, from the viewpoint of further suppressing the occurrence of uneven plating and contamination of the plating solution. More specifically, a methyl group, an ethyl group, a propyl group, a butyl group, etc. are mentioned.
  • the aryl group include a carbocyclic aryl group (aromatic hydrocarbon group) and a heterocyclic aryl group (aromatic heterocyclic group).
  • the carbocyclic aryl group include groups having 6 to 19 carbon atoms (for example, a phenyl group, a naphthyl group, an anthracenyl group, and a pyrenyl group) from the viewpoint that the effects of the present invention are more excellent.
  • the heterocyclic aryl group has 3 to 20 carbon atoms and 1 to 5 hetero atoms (for example, a pyridyl group, a furyl group, a quinolyl group condensed with a benzene ring, benzofuryl group, thioxanthone group, the group of carbazole group) preferably.
  • R 1 , R 2 and R 3 may be bonded to form a ring.
  • the type of ring to be formed is not particularly limited, but an aliphatic hydrocarbon ring is preferable, and a 4- to 6-membered ring is particularly preferable from the viewpoint of suppressing the occurrence of uneven plating and contamination of the plating solution.
  • the ring formed may form a ring via —O— group, —S— group, —CO— group, or —NR 4 — group.
  • R 4 represents a hydrogen atom or an alkyl group (preferably having 8 or less carbon atoms. For example, a methyl group, an ethyl group, a propyl group, etc.).
  • alkyl groups such as methyl and ethyl groups (preferably having 1 to 20 carbon atoms); aryl groups such as phenyl and naphthyl groups (preferably having 6 to 16 carbon atoms); sulfonamido groups and N-sulfonylamides Group, acyloxy group such as acetoxy group (preferably 1 to 6 carbon atoms); alkoxy group such as methoxy group and ethoxy group (preferably 1 to 6 carbon atoms); dimethylamino group, diethylamino group, t-butylamino group Alkylamino groups such as groups (preferably having 1 to 8 carbon atoms); halogen atoms such as chlorine and bromine; alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group and cyclohex
  • R 1 , R 2, and R 3 are preferably formed as R 1 is an alkyl group having 1 to 8 carbon atoms in terms of better polarity conversion efficiency and better adhesion to the metal layer.
  • 2 is an alkyl group having 1 to 8 carbon atoms
  • R 3 is an alkyl group having 1 to 8 carbon atoms, a carbocyclic aryl group having 6 to 19 carbon atoms, and an alkyl group having 1 to 6 carbon atoms.
  • R 2 and R 3 may be bonded to form a 4- to 6-membered aliphatic hydrocarbon ring.
  • Preferred embodiments of the polar conversion group A include an embodiment having a group represented by the following general formula (2). * Indicates a binding position.
  • R 5 and R 6 represent a hydrogen atom, an alkyl group that may have a substituent, or an aryl group that may have a substituent, and at least one of R 5 and R 6 Represents an aryl group.
  • the definition and preferred range of the alkyl group are the same as those of the alkyl group represented by R 1 , R 2 and R 3 described above.
  • Examples of the aryl group include the aryl groups represented by R 1 , R 2 , and R 3 described above.
  • the type of alkyl group and the substituent which may be substituted on the aryl group is as described above.
  • R 5 and R 6 may combine to form a ring. Examples of the ring formed include the rings formed by R 1 , R 2 , and R 3 described above.
  • R 5 is an alkyl group having 1 to 8 carbon atoms or 6 to 19 carbon atoms in that the efficiency of polarity conversion is better and the adhesion to the metal layer is better.
  • R 6 is a carbocyclic ring having 6 to 19 carbon atoms
  • Preferred embodiments of the polar conversion group A include an embodiment having a group represented by the following general formula (3). * Indicates a binding position.
  • R 7 represents a hydrogen atom or an alkyl group which may have a substituent.
  • the definition and preferred range of the alkyl group are the same as those of the alkyl group represented by R 1 , R 2 and R 3 described above.
  • the types of substituents that may be substituted on the alkyl group are also as described above.
  • R 8 represents an alkyl group which may have a substituent.
  • the definition and preferred range of the alkyl group are the same as those of the alkyl group represented by R 1 , R 2 and R 3 described above.
  • the types of substituents that may be substituted on the alkyl group are also as described above.
  • R 7 and R 8 may combine to form a ring. Examples of the ring formed include the rings formed by R 1 , R 2 , and R 3 described above.
  • R 7 and R 8 is an alkyl group substituted with an electron-withdrawing group such as an alkoxy group, an alkoxycarbonyl group, or a halogen group in view of better stability over time and alkali resistance. preferable. Further, as other preferred embodiments of R 7 and R 8 , R 7 is an alkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms having an alkoxy group having 1 to 6 carbon atoms, or 2 to 7 carbon atoms.
  • R 8 is an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 6 carbon atoms
  • R 7 and R 8 may combine to form a 4- to 6-membered aliphatic hydrocarbon ring.
  • Preferred embodiments of the polar conversion group A include an embodiment having a group represented by the following general formula (4). * Indicates a binding position.
  • R 9 and R 10 represent an alkyl group which may have a substituent or an aryl group which may have a substituent.
  • the alkyl group preferably has 1 to 25 carbon atoms and more preferably 1 to 8 carbon atoms from the viewpoint that the effects of the present invention are more excellent. More specifically, a linear, branched or cyclic alkyl group such as a methyl group, an ethyl group, an isopropyl group, a t-butyl group and a cyclohexyl group can be mentioned.
  • the aryl group include the aryl groups represented by R 1 , R 2 , and R 3 described above.
  • R 9 and R 10 may combine to form a ring.
  • Examples of the ring formed include the rings formed by R 1 , R 2 , and R 3 described above.
  • the type of the substituent is not particularly limited as long as the effects of the present invention are not impaired.
  • the alkyl represented by the above-described R 1 , R 2 , and R 3 Examples include a substituent substituted with a group or an aryl group.
  • an alkyl group substituted with an electron-withdrawing group such as an alkoxy group, a carbonyl group, an alkoxycarbonyl group, a cyano group, a halogen group, or a cyclohexyl group is preferable in terms of stability over time.
  • a cyclic alkyl group such as a norbornyl group is particularly preferable.
  • a compound in which the chemical shift of secondary methine hydrogen in proton NMR in a deuterated chloroform appears in a magnetic field lower than 4.4 ppm is preferable, and a compound that appears in a magnetic field lower than 4.6 ppm is more preferable.
  • an alkyl group substituted with an electron-withdrawing group is particularly preferred because the carbocation that appears to be formed as an intermediate during the thermal decomposition reaction is destabilized by the electron-withdrawing group and decomposition is suppressed. This is considered to be because of this.
  • the structure represented by the following formula is particularly preferable as the structure of —CHR 9 R 10 .
  • the polar conversion group may have a group other than the group represented by any one of the general formulas (1) to (4) described above.
  • a linking group —L— may be further bonded to * in the general formulas (1) to (4).
  • the linking group is not particularly limited, and examples thereof include divalent to tetravalent linking groups. For example, 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 20 sulfur atoms. Examples include groups consisting of atoms. More specific examples of the linking group include the following structural units and groups constituted by combining them. In addition, these coupling groups may have a substituent.
  • the type of the substituent is not particularly limited, and examples thereof include a substituent substituted with the alkyl group or aryl group represented by R 1 , R 2 , and R 3 described above.
  • (B) Polarity converting group B As the polarity converting group B, a known functional group can be used. For example, a functional group whose hydrophilicity / hydrophobicity is changed by irradiation with light of 700 nm or less can be used. In this way, functional groups that undergo polarity conversion upon irradiation with light of 700 nm or less can directly undergo decomposition, ring opening, or dimerization reaction upon irradiation with light of a predetermined wavelength, regardless of long-wavelength exposure such as infrared rays or heat. in, wherein the hydrophilic changes from hydrophobic at high sensitivity.
  • the functional group for example, functional groups represented by general formulas (a) to (i) described in JP-A No. 2004-175098 can be used.
  • the crosslinkable group contained in the polymer is a crosslinkable group highly resistant to an alkaline aqueous solution described later, and specifically includes a carboxyl group (—COOH), a hydroxyl group, an isocyanate group, an alkoxysilyl group, an acetoxysilyl group, a chlorosilyl group.
  • a to-be-plated layer having high resistance to an alkaline aqueous solution can be obtained, and plating unevenness and plating solution contamination during plating are suppressed.
  • an epoxy group, an oxetanyl group, a hydroxyl group, or an alkoxysilyl group is preferable in that the occurrence of uneven plating can be further suppressed.
  • the alkoxysilyl group is a silyl group having an alkoxy group.
  • it means a group in which an alkoxy group is bonded to a silicon atom (—Si—OR d (R d : alkyl group), specifically, a trialkoxysilyl group, an alkyl dialkoxysilyl group, etc.
  • Acetoxy A silyl group means a group in which an acetoxy group is bonded to a silicon atom
  • a chlorosilyl group means a group in which a chlorine atom is bonded to a silicon atom.
  • the type of the skeleton of the polymer having the polar functional group and the crosslinkable group is not particularly limited.
  • polyimide resin, epoxy resin, urethane resin, polyethylene resin, polyester resin, urethane resin, novolac resin, cresol resin, acrylic resin, A methacrylic resin, a styrene resin, etc. are mentioned.
  • acrylic resins and methacrylic resins are preferable in terms of availability of materials and film formability.
  • the polymer containing the unit represented by the following general formula (A) is mentioned as a unit which has a polar conversion group.
  • the polymer has a unit represented by the general formula (A)
  • the occurrence of uneven plating and contamination of the plating solution can be further suppressed.
  • R 11 represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms.
  • the alkyl group include a methyl group and an ethyl group.
  • L 1 represents a single bond or a divalent organic group.
  • the divalent organic group include a substituted or unsubstituted divalent aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms, for example, an alkylene group such as a methylene group, an ethylene group, and a propylene group), a substituted or unsubstituted group.
  • a divalent aromatic hydrocarbon group (preferably having 6 to 12 carbon atoms, such as a phenylene group), —O—, —S—, —SO 2 —, —N (R) — (R: alkyl group), And —CO—, —NH—, —COO—, —CONH—, or a combination thereof (for example, an alkyleneoxy group, an alkyleneoxycarbonyl group, an alkylenecarbonyloxy group, and the like).
  • a single bond and an aromatic hydrocarbon group are preferable at the point which the effect of this invention is more excellent.
  • Y represents the polar conversion group described above.
  • a group represented by any one of the general formulas (1) to (4) is preferable in that the occurrence of uneven plating and contamination of the plating solution can be further suppressed.
  • the unit represented by the general formula (A) is preferable in that the occurrence of uneven plating and contamination of the plating solution can be further suppressed. Can be mentioned.
  • L 2 represents a single bond, an amide group (—CONH—), an ester group, or a phenylene group.
  • L 3 represents a single bond or an aliphatic hydrocarbon group. Note that when L 2 is an amide group or an ester group, L 3 represents an aliphatic hydrocarbon group.
  • the content of the unit represented by the general formula (A) in the polymer (or the unit represented by the general formula (A-1)) is not particularly limited, but the occurrence of uneven plating and contamination of the plating solution are further suppressed.
  • the total polymer unit is preferably 10 to 95 mol%, more preferably 55 to 90 mol%.
  • Another preferred embodiment of the polymer having a polar conversion group and a specific crosslinkable group includes a polymer containing a unit represented by the following general formula (B) as the unit having a crosslinkable group.
  • B a unit represented by the following general formula (B)
  • the occurrence of uneven plating and contamination of the plating solution can be further suppressed.
  • R 12 represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms.
  • alkyl group include a methyl group and an ethyl group.
  • L 4 represents a single bond or a divalent organic group. Definition of the organic groups are the same as those defined organic group represented by L 1.
  • Z is a carboxyl group, hydroxyl group, isocyanate group, alkoxysilyl group, acetoxysilyl group, chlorosilyl group, primary amino group, secondary amino group, tertiary amino group, epoxy group, oxetanyl group.
  • R 13 to R 15 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms.
  • alkyl group include a methyl group and an ethyl group.
  • R 16 is a hydrogen atom, an alkyl group (preferably having 1 to 8 carbon atoms), an alkenyl group (preferably having 1 to 8 carbon atoms), an alkynyl group (preferably having 1 to 8 carbon atoms), Or represents an aryl group. Among them, in terms of the effect of the present invention is more excellent, an alkyl group, an aryl group are more preferable.
  • the unit represented by the general formula (B) is preferable in that the occurrence of uneven plating and contamination of the plating solution can be further suppressed. Can be mentioned.
  • L 5 represents a single bond, an amide group, an ester group, or a phenyl group.
  • L 6 represents a single bond or an aliphatic hydrocarbon group which may be interposed via a —O—, —COO— or —CONH— bond.
  • Z is a carboxyl group, L 5 and L 6 may both be single bonds.
  • the method for synthesizing the polymer having a polar converting group and a crosslinkable group is not particularly limited, and a known method (for example, radical polymerization, cationic polymerization, etc.) can be used.
  • a method of copolymerizing a monomer having a polarity converting group and a monomer having a crosslinkable group can be mentioned.
  • the monomer having a polarity conversion group to be used include the following monomers.
  • Examples of the monomer having a crosslinkable group used include the following monomers.
  • a polymer can be synthesized by referring to a method described in JP-A-2009-007540.
  • a preferable embodiment of the polymer having a polar conversion group and a crosslinkable group is a polymer synthesized by copolymerizing the monomer having the polar conversion group and the monomer having the crosslinkable group. Specific examples are shown below, but are not limited to these polymers. In addition, the numerical value written together by the repeating unit in the polymer shown below shows mol% of each unit.
  • the content of the polymer in the composition for forming a plated layer is not particularly limited, but is preferably 2 to 50% by mass, more preferably 5 to 30% by mass with respect to the total amount of the composition. If it is in the said range, it is excellent in the handleability of a composition and it is easy to control the layer thickness of a to-be-plated layer.
  • solvent to be plated layer forming composition, if desired, it may contain a solvent.
  • solvents that can be used include alcohol solvents such as water, methanol, ethanol, propanol, ethylene glycol, glycerin, and propylene glycol monomethyl ether; acids such as acetic acid; ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; formamide and dimethyl Amide solvents such as acetamide and N-methylpyrrolidone; Nitrile solvents such as acetonitrile and propionitrile; Ester solvents such as methyl acetate, ethyl acetate and propylene glycol monomethyl ether acetate; Carbonates such as dimethyl carbonate and diethyl carbonate A solvent is mentioned. Further, a solvent having a boiling point of 50 ° C. to 150 ° C. is preferable for ease of handling. Incidentally, the these solvents may be used singly,
  • the composition for forming a layer to be plated may contain a cross-linking agent having a reactive functional group that reacts with the cross-linkable group described above, if necessary.
  • a cross-linking agent By including the cross-linking agent, a chemical bond is formed with the cross-linkable group in the above-described polymer, and the resistance of the plated layer to the alkaline aqueous solution is further improved.
  • the crosslinking agent usually has 2 or more reactive functional groups that react with the crosslinkable group, and preferably has 2 to 6 reactive functional groups.
  • the reactive functional group include a hydroxyl group, an isocyanate group, a carboxylic acid group, an epoxy group, a carboxylic anhydride group, a primary amino group, a secondary amino group, an alkoxysilyl group, and a benzyl halide group.
  • crosslinkable group, reactive functional group (carboxyl group, primary or secondary amino group), (carboxyl group) , Aziridine group), (carboxyl group, isocyanate group), (carboxyl group, epoxy group), (carboxyl group, halogenated benzyl group), (primary or secondary amino group, isocyanate group), (primary, secondary, or Tertiary amino group, halogenated benzyl group), (primary amino group, aldehydes), (isocyanate group, primary or secondary amino group), (isocyanate group, isocyanate group), (isocyanate group, hydroxyl group), (isocyanate group) , Epoxy group), (hydroxyl group, isocyanate group), (hydroxyl group, benzyl halide group) , (Hydroxyl group, carboxylic acid anhydride group
  • crosslinkable group, reactive functional group (epoxy group, amino group), (epoxy group, epoxy group), (tertiary amino group) in terms of suppressing the occurrence of uneven plating and contamination of the plating solution.
  • Group, halogenated benzyl group), (hydroxyl group, isocyanate group), (oxetanyl group, epoxy group), and (alkoxysilyl group, alkoxysilyl group) are more preferred combinations.
  • crosslinking agent examples include the following crosslinking agents.
  • the amount of the crosslinking agent used in the composition for forming a layer to be plated is usually preferably from 0.01 to 50 equivalents, more preferably from 0.01 to 10 equivalents, more preferably from 0.1 to 10 equivalents per mole of the crosslinkable group. More preferred is 5 to 3 equivalents.
  • the usage-amount of a crosslinking agent is in the said range, it will become easy to osmose
  • the composition for forming a layer to be plated may contain a photoacid generator, if necessary.
  • a photoacid generator is contained in the composition for forming a layer to be plated, an acid can be supplied into the layer to be plated by light irradiation in the step (C) described later.
  • photoacid generator for example, known compounds (for example, a photoinitiator for photocationic polymerization, a photoinitiator for radical photopolymerization, a photodecolorant for dyes, etc.) can be used.
  • known compounds for example, a photoinitiator for photocationic polymerization, a photoinitiator for radical photopolymerization, a photodecolorant for dyes, etc.
  • onium salt compounds such as iodonium salts and sulfonium salts.
  • the content of the photoacid generator in the composition for forming a layer to be plated is not particularly limited, but is preferably about 0.001 to 40% by mass, preferably 0.01 to 20% by mass with respect to the total solid content of the composition. Is more preferable, and 0.1 to 5% by mass is even more preferable. If it is in the said range, in the process (C) mentioned later, the polarity conversion of a functional group will progress more efficiently.
  • the composition for forming a layer to be plated includes a surfactant, a plasticizer, a polymerization inhibitor, a polymerization initiator for proceeding with curing, a curing accelerator, and a rubber component (for example, CTBN). ), Flame retardants (for example, phosphorus flame retardants), diluents, thixotropic agents, pigments, antifoaming agents, leveling agents, coupling agents and the like.
  • the composition for forming a layer to be plated has a polymerizable group and a catalyst adsorbing group described in JP2009-7540A or JP2010-248464A as long as the effects of the present invention are not impaired. It may contain a polymer.
  • the first embodiment of the laminate manufacturing method of the present invention includes a step (A) of forming a layer to be plated on the surface of the substrate, a step (B) of bringing the layer to be plated into contact with an alkaline aqueous solution, Performing a treatment to convert a functional group in the layer to be plated from hydrophobic to hydrophilic (C), applying a plating catalyst or a precursor thereof to the layer to be plated (D), and performing a plating treatment And a step (E).
  • a step (A) of forming a layer to be plated on the surface of the substrate
  • a step (B) of bringing the layer to be plated into contact with an alkaline aqueous solution Performing a treatment to convert a functional group in the layer to be plated from hydrophobic to hydrophilic (C), applying a plating catalyst or a precursor thereof to the layer to be plated (D), and performing a plating treatment And a step (E).
  • a process (A) is a process of forming a to-be-plated layer on the surface of a board
  • a layer to be plated to which a plating catalyst or the like to be described later is applied is formed. More specifically, in this step, a substrate 10 is prepared as shown in FIG. 1A, and a layer 12 to be plated is formed on the surface of the substrate 10 as shown in FIG.
  • the layer to be plated formed in this step changes the hydrophilicity / hydrophobicity of the polarity conversion group from hydrophobic to hydrophilic by heating, supply of acid, or irradiation of radiation.
  • the hydrophilicity / hydrophobicity of is also changed to more hydrophilic. That is, it preferably changes from a hydrophobic plated layer to a hydrophilic plated layer.
  • the layer to be plated since the layer to be plated exhibits hydrophilicity after contact with an alkaline aqueous solution, it efficiently adsorbs a plating catalyst or a precursor thereof described later. That is, the layer to be plated functions as a good receiving layer for the plating catalyst (or its precursor).
  • the substrate is a member for supporting each layer described later, and any conventionally known substrate (for example, a resin substrate, a ceramic substrate, a glass substrate, a metal substrate, etc., preferably an insulating substrate) is used. be able to.
  • any conventionally known substrate for example, a resin substrate, a ceramic substrate, a glass substrate, a metal substrate, etc., preferably an insulating substrate.
  • metal plates eg, aluminum, zinc, copper, etc.
  • plastic films eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene terephthalate, polyethylene
  • Polystyrene polypropylene, polycarbonate, polyvinyl acetal, polyimide, epoxy resin, and the like
  • plastic films on which the above metal is laminated or vapor-deposited.
  • substrate may have metal wiring in the inside or one side or both surfaces.
  • the metal wiring may be formed in a pattern with respect to the surface of the substrate or may be formed on the entire surface. Typically, those formed by a subtractive method using an etching process and those formed by a semi-additive method using electrolytic plating may be used, and those formed by any method may be used. Examples of the material constituting the metal wiring include copper, silver, tin, palladium, gold, nickel, chromium, tungsten, indium, zinc, and gallium.
  • the method for forming the layer to be plated on the substrate is not particularly limited, and a known method can be adopted.
  • a method for forming a layer to be plated (coating method) by applying a composition for forming a layer to be plated on the substrate, and a film of the layer to be plated formed from the composition for forming a layer to be plated directly on the substrate.
  • the method of laminating etc. is mentioned.
  • the coating method is preferable from the point that the film thickness control of a to-be-plated layer is easy.
  • the aspect of the coating method will be described in detail.
  • the method for applying the composition for forming a layer to be plated on the substrate is not particularly limited, and a known method (for example, spin coating, dip coating, double roll coater, slit coater, air knife coater, wire bar coater, etc.) should be used. Can do. From the viewpoint of handleability and production efficiency, an embodiment in which the composition for forming a layer to be plated is applied on a substrate, and if necessary, is subjected to a drying treatment to remove the contained solvent to form a layer to be plated. .
  • the thickness of the layer to be plated is not particularly limited, but is preferably 0.02 to 5.0 ⁇ m, more preferably 0.05 to 2.0 ⁇ m, from the viewpoint of better adhesion of the metal layer.
  • the content of the polymer in the layer to be plated is not particularly limited, but is preferably 10 to 100% by mass, and preferably 50 to 100% by mass with respect to the total amount of the layer to be plated, from the viewpoint of better adhesion of the metal layer. It is more preferable that
  • the layer to be plated is preferably a layer obtained by curing a polymer having a polarity converting group and a crosslinkable group by a crosslinking reaction.
  • the curing of the layer proceeds via the crosslinkable group, the film strength of the layer to be plated itself is increased, the hydrophobicity is also increased, and the resistance to the aqueous alkali solution is improved.
  • the aspect of the step (G) will be described in detail.
  • a hardening process (process (G)) after this process (A), and before the process (D) mentioned later. More specifically, it is between step (A) and step (B), between step (B) and step (C), or between step (C) and step (D).
  • a process (G) between a process (A) and a process (B) at the point which can suppress the elution and decomposition
  • an optimum method is appropriately selected depending on the kind of the crosslinkable group in the polymer, and examples thereof include a method of reacting crosslinkable groups with each other and a method of using a crosslinking agent. .
  • the method of reacting crosslinkable groups is a method of forming a crosslinked structure in the layer to be plated through an addition reaction or a condensation reaction between the crosslinkable groups.
  • the crosslinkable group is —NCO
  • a self-condensation reaction can be advanced by applying heat to form a crosslinked structure in the layer to be plated.
  • a method using a crosslinking agent is a method in which a crosslinkable group in a polymer is reacted with a reactive functional group of a crosslinker having a reactive functional group that reacts with the above-described crosslinkable group. It is a method of forming.
  • the type of curing treatment varies depending on the type of polymer used and the crosslinking agent, and an optimum treatment method is appropriately selected.
  • heat treatment or exposure treatment is carried out.
  • the heating temperature is preferably from 50 to 200 ° C., more preferably from 80 to 150 ° C., from the viewpoint of suppressing the decomposition of the polarity converting group and productivity.
  • the treatment time is preferably 2 to 60 minutes, more preferably 5 to 30 minutes.
  • the type of light to be irradiated is not particularly limited, but ultraviolet light or visible light is preferably used.
  • the irradiation energy is preferably from 100 to 10,000 mJ, more preferably from 500 to 5000 mJ, from the viewpoint of productivity.
  • a process (B) is a process of making a to-be-plated layer and alkaline aqueous solution contact after the said process (A).
  • the organic adsorbate on the layer to be plated is removed, and as a result, the uniformity of plating is improved.
  • the penetration of the plating catalyst described later is promoted by increasing the wettability of the layer to be plated.
  • the material (alkali aqueous solution etc.) used at this process is explained in full detail first, and the procedure of the post process is explained in full detail.
  • the type of the aqueous alkali solution used in the step (B) is not particularly limited as long as the pH is alkaline.
  • the pH of the alkaline aqueous solution is preferably 10 to 14, and more preferably 12 to 14 in terms of suppressing the occurrence of uneven plating and contamination of the plating solution.
  • Water is usually used as the solvent used in the alkaline aqueous solution.
  • organic solvents such as methanol, ethanol, propanol, ethylene glycol, glycerin and propylene glycol monomethyl ether, acids such as acetic acid, hydroxyacetic acid and aminocarboxylic acid, ketones such as acetone and methyl ethyl ketone
  • Solvents amide solvents such as formamide, dimethylacetamide, N-methylpyrrolidone, nitrile solvents such as acetonitrile and propionitrile, carbonate solvents such as dimethyl carbonate and diethyl carbonate, glycol solvents, etc.
  • amide solvents such as formamide, dimethylacetamide, N-methylpyrrolidone
  • nitrile solvents such as acetonitrile and propionitrile
  • carbonate solvents such as dimethyl carbonate and diethyl carbonate, glycol solvents, etc.
  • the type of the alkaline aqueous solution is not particularly limited, and examples thereof include a lithium hydroxide aqueous solution, a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, a lithium carbonate aqueous solution, a sodium carbonate aqueous solution, a potassium carbonate aqueous solution, a lithium hydrogen carbonate aqueous solution, and a sodium hydrogen carbonate aqueous solution.
  • Examples include aqueous solutions, potassium hydrogen carbonate aqueous solutions, calcium hydroxide aqueous solutions, strontium hydroxide aqueous solutions, barium hydroxide aqueous solutions, calcium carbonate aqueous solutions, strontium carbonate aqueous solutions, and barium carbonate aqueous solutions.
  • the content of the alkali component (inorganic base) is preferably adjusted to a range where the pH is in the above range.
  • a surfactant may be added to the alkaline aqueous solution.
  • the type of the surfactant used is not particularly limited, and examples thereof include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant.
  • anionic surfactant examples include alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl ether sulfate, alkyl or alkenyl ether carboxylate, amino acid type surfactant, N- Examples include acylamino acid type surfactants, alkyl or alkenyl phosphate esters and salts thereof.
  • Nonionic surfactants include, for example, polyoxyalkylene alkyls or alkenyl ethers, polyoxyethylene alkyl phenyl ethers, higher fatty acid alkanolamides or alkylene oxide adducts thereof, sucrose fatty acid esters, alkyl glycoxides, fatty acid glycerin monoesters, Examples include alkylamine oxide.
  • Examples of the cationic surfactant include alkyl cationic surfactants, amide type quaternary cationic surfactants, ester type quaternary cationic surfactants, and the like.
  • Examples of amphoteric surfactants include carboxyl-type amphoteric surfactants and sulfobetaine-type amphoteric surfactants.
  • step (B) The contact method of a to-be-plated layer and aqueous alkali solution is not restrict
  • the temperature of the aqueous alkaline solution at the time of contact is not particularly limited, but is preferably in the range of 30 ° C. to 90 ° C., more preferably in the range of 50 ° C. to 70 ° C. in terms of suppressing the occurrence of uneven plating and contamination of the plating solution. preferable.
  • the contact time between the layer to be plated and the aqueous alkaline solution is preferably in the range of 5 seconds to 30 minutes, more preferably in the range of 30 seconds to 25 minutes, from the viewpoint that the occurrence of uneven plating and contamination of the plating solution can be further suppressed. A range of ⁇ 20 minutes is more preferred.
  • Step (C) is a step of converting the polarity conversion group from hydrophobic to hydrophilic by performing heating, acid supply, or irradiation with radiation after the step (B). More specifically, by performing the treatment, the contact angle with the water of the layer to be plated after the treatment is lower than the contact angle with the water of the layer to be plated before the treatment. That is, the treatment changes the hydrophilicity / hydrophobicity of the layer to be plated so that the contact angle with water decreases. By carrying out this step, the layer to be plated is converted from hydrophobic to hydrophilic, and the affinity for the plating catalyst or its precursor is improved.
  • transmittance of the plating catalyst liquid used at the catalyst provision process mentioned later and the plating liquid used at a plating process improves, As a result, the adhesiveness of a metal layer improves.
  • the treatment performed in this step is appropriately performed appropriately depending on the type of polarity conversion group in the layer to be plated. Below, each procedure is explained in full detail. In addition, you may implement the following polarity conversion processes in a pattern form as needed. That is, the pattern of the hydrophilic region and the hydrophobic region may be formed on the surface of the layer to be plated by performing imagewise heating, acid supply, or irradiation with radiation.
  • the conditions for the heat treatment are not particularly limited, but the heating temperature is preferably 100 to 250 ° C., more preferably 150 to 200 ° C., from the viewpoint of the heat resistance of the layer to be plated and the good polarity conversion efficiency of the polarity conversion group.
  • the heating time is preferably 1 minute to 1 hour, more preferably 5 minutes to 30 minutes from the viewpoint of productivity and good polarity conversion efficiency of the polarity conversion group.
  • a well-known apparatus for example, a ventilation dryer, oven, an infrared dryer, a heating drum etc.
  • the method for supplying the acid is not particularly limited.
  • the method of generating an acid is mentioned.
  • the pH of the acidic solution is not particularly limited, but is preferably 3 or less, more preferably 1 or less, from the viewpoint of good polarity conversion efficiency of the polarity conversion group.
  • the kind of the acidic component in the acidic solution is not particularly limited, and known acids such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, paratoluenesulfonic acid, methanesulfonic acid, and trifluoroacetic acid can be used.
  • the acid content in the acidic solution is preferably about 5 to 50% by mass, more preferably 10 to 40% by mass, from the viewpoint of good polarity conversion efficiency of the polar conversion group.
  • the type of the solvent in the acidic solution is not particularly limited, and for example, water or an organic solvent is used.
  • the method for bringing the acidic solution into contact with the layer to be plated is not particularly limited, and examples thereof include a method of applying the acidic solution on the layer to be plated and a method of immersing a substrate having the layer to be plated in the acidic solution.
  • the contact time between the acidic solution and the layer to be plated is not particularly limited, but is preferably 1 minute to 1 hour and more preferably 5 minutes to 30 minutes from the viewpoint of productivity and good polarity conversion efficiency of the polarity conversion group.
  • the liquid temperature of the acidic solution at the time of contact is not particularly limited, but is preferably 30 to 95 ° C., more preferably 40 to 90 ° C. from the viewpoint of productivity and good polarity conversion efficiency of the polarity conversion group.
  • the photoacid generator used is a known compound (for example, a photoinitiator for photocationic polymerization, a photoinitiator for radical photopolymerization, a photodecolorant for dyes, etc.). Can be used.
  • the content of the photoacid generator in the layer to be plated is preferably about 0.001 to 40% by mass, more preferably 0.01 to 20% by mass, and preferably 0.1% to the total solid content of the layer to be plated. More preferably, it is ⁇ 5% by mass.
  • the method for supplying the photoacid generator into the layer to be plated is not particularly limited, and examples thereof include a method of forming the layer to be plated by adding the photoacid generator to the above-described composition for forming a layer to be plated.
  • the method in particular of generating an acid from the photo-acid generator in a to-be-plated layer is not restrict
  • the conditions for the heat treatment the above-mentioned conditions are preferably exemplified.
  • the conditions for the exposure process include conditions for a radiation irradiation process described later.
  • the type of radiation used is not particularly limited, and radiation in the optimum wavelength range is used according to the type of polarity conversion group. Especially, it is preferable to use ultraviolet light or visible light from the point which performs the polarity conversion of a polarity conversion group more efficiently.
  • the irradiation time varies depending on the reactivity of the polar conversion group and the type of the light source, but is preferably 10 seconds to 5 hours from the viewpoint of productivity.
  • the exposure energy is preferably about 10 to 8000 mJ, more preferably 100 to 3000 mJ.
  • the said heating, supply of an acid, and a radiation irradiation process may implement 2 or more processes at a process (C).
  • the hydrophilicity / hydrophobicity of the polarity conversion group in the layer to be plated is changed by performing the above-described treatment, and as a result, the hydrophilicity / hydrophobicity of the layer to be plated is changed from hydrophobic to hydrophilic. That is, it preferably changes from a hydrophobic plated layer to a hydrophilic plated layer.
  • the to-be-plated layer before polarity conversion shows hydrophobicity
  • the water contact angle is preferably 70 ° or more, more preferably 80 ° or more from the viewpoint of better resistance to an aqueous alkali solution.
  • the upper limit is not particularly limited, but is usually 120 ° or less.
  • the layer to be plated after polarity conversion usually exhibits hydrophilicity, and the water contact angle is preferably less than 70 °, more preferably 50 ° or less, from the viewpoint of better affinity for the plating catalyst and the like.
  • the converted polarity conversion group is a carboxylic acid group, a sulfonic acid group, or a sulfinic acid group
  • the layer to be plated after the polarity conversion contains these acid groups when an alkaline plating solution is used. By being salted to form a salt, the hydrophilicity is further increased and the penetration of the plating solution can be further promoted.
  • a layer to be plated having a water contact angle of 70 ° or more is referred to as a hydrophobic layer and a layer to be plated that is less than 70 ° is referred to as a hydrophilic layer.
  • a method for measuring the water contact angle a tangential method using two points of contact between the top of the dropped water and the substrate is used.
  • a process (D) is a process of providing a plating catalyst or its precursor to the to-be-plated layer obtained at the process (C).
  • a plating catalyst or a precursor thereof is applied to a layer to be plated that exhibits hydrophilicity (hydrophilic layer to be plated).
  • the polar conversion group converted to hydrophilicity is a carboxylic acid group, a sulfonic acid group, or a sulfinic acid group
  • the plating catalyst or precursor thereof to which these groups are attached is efficiently attached (adsorbed).
  • plating catalyst or its precursor functions as a catalyst or electrode for plating treatment in the plating step described later. Therefore, the type of plating catalyst or precursor used is appropriately determined depending on the type of plating treatment. In addition, it is preferable that the plating catalyst used or its precursor is an electroless plating catalyst or its precursor from the point which improves the uniformity of plating.
  • electroless plating or a precursor thereof will be described in detail.
  • any catalyst can be used as long as it becomes an active nucleus at the time of electroless plating.
  • a metal having a catalytic ability for autocatalytic reduction reaction which tends to be more ionized than Ni.
  • metals capable of low electroless plating More specifically, Pd, Ag, Cu, Ni, Al, Fe, Co, etc. are mentioned. Of these, Ag and Pd are particularly preferable because of their high catalytic ability.
  • metal colloid metal particles
  • a metal colloid can be prepared by reducing metal ions in a solution containing a charged surfactant or a charged protective agent.
  • the electroless plating catalyst precursor can be used without particular limitation as long as it can become an electroless plating catalyst by a chemical reaction.
  • the metal ions of the metals mentioned as the electroless plating catalyst are mainly used.
  • the metal ion that is an electroless plating catalyst precursor becomes a zero-valent metal that is an electroless plating catalyst by a reduction reaction.
  • the metal ion that is an electroless plating catalyst precursor may be used as an electroless plating catalyst after being applied to the layer to be plated and before being immersed in the electroless plating solution, by separately changing to a zero-valent metal by a reduction reaction.
  • the electroless plating catalyst precursor may be immersed in an electroless plating solution and changed to a metal (electroless plating catalyst) by a reducing agent in the electroless plating solution.
  • the metal ion that is the electroless plating catalyst precursor is preferably applied to the layer to be plated using a metal salt.
  • the metal salt used is not particularly limited as long as it is dissolved in a suitable solvent and dissociated into a metal ion and a base (anion), and M (NO 3 ) n , MCl n , M 2 / n (SO 4 ), M 3 / n (PO 4 ) (M represents an n-valent metal atom), and the like.
  • a metal ion the thing which said metal salt dissociated can be used suitably. Specific examples include, for example, Ag ions, Cu ions, Al ions, Ni ions, Co ions, Fe ions, and Pd ions. Among them, those capable of multidentate coordination are preferable, and in particular, functionalities capable of coordination. In view of the number of types of groups and catalytic ability, Ag ions and Pd ions are preferred.
  • zero-valent metals other than those described above can also be used as a catalyst used for direct electroplating without electroless plating.
  • the plating catalyst or a precursor thereof is preferably used in the form of a solution in which these are dispersed or dissolved in a solvent (hereinafter also referred to as a plating catalyst solution as appropriate). That is, the plating catalyst solution contains a plating catalyst or a precursor thereof.
  • the plating catalyst solution usually contains a solvent, and an organic solvent and / or water is used as the type of solvent. Usually, water is used as the main component.
  • the plating catalyst liquid contains an organic solvent, the permeability of the plating catalyst liquid to the layer to be plated is improved, and the plating catalyst or its precursor can be efficiently adsorbed to the layer to be plated.
  • the organic solvent used in the plating catalyst solution is not particularly limited as long as it is a solvent that can penetrate into the plating layer. Specifically, acetone, methyl acetoacetate, ethyl acetoacetate, ethylene glycol diacetate, cyclohexanone, Acetylacetone, acetophenone, 2- (1-cyclohexenyl) cyclohexanone, propylene glycol diacetate, triacetin, diethylene glycol diacetate, dioxane, N-methylpyrrolidone, dimethyl carbonate, dimethyl cellosolve, and the like can be used.
  • the method for applying the plating catalyst or its precursor to the layer to be plated is not particularly limited.
  • a plating catalyst solution containing a plating catalyst or a precursor thereof (a dispersion in which a metal is dispersed in an appropriate dispersion medium or a solution containing a dissociated metal ion in which a metal salt is dissolved in an appropriate solvent) is prepared.
  • a method of applying a plating catalyst solution on the layer to be plated, or a method of immersing a substrate on which the layer to be plated is formed in the plating catalyst solution.
  • the contact time between the layer to be plated and the plating catalyst solution is preferably about 30 seconds to 10 minutes, and more preferably about 3 minutes to 5 minutes.
  • the temperature of the plating catalyst solution at the time of contact is preferably about 20 to 60 ° C., more preferably about 30 to 50 ° C.
  • the step (E) is a step of forming a metal layer (plating layer) on the layer to be plated by performing a plating process on the layer to be plated to which the plating catalyst or its precursor is applied in the step (D). is there. More specifically, by performing this step, as shown in FIG. 1C, the metal layer 14 is provided on the layer 12 to be plated, and the laminate 16 is obtained.
  • Examples of the plating treatment performed in this step include electroless plating and electrolytic plating.
  • the plating treatment can be selected depending on the function of the plating catalyst applied to the layer to be plated or its precursor. Especially, it is preferable to perform electroless plating from the point of the adhesive improvement of the metal layer formed. Further, in order to obtain a metal layer having a desired layer thickness, it is a more preferable aspect that electrolytic plating is further performed after electroless plating.
  • the plating suitably performed in this process will be described.
  • Electroless plating refers to an operation of depositing a metal by a chemical reaction using a solution in which metal ions to be deposited as a plating are dissolved.
  • the substrate to which the electroless plating catalyst has been applied is washed with water to remove excess electroless plating catalyst (metal) from the layer to be plated, and then immersed in an electroless plating bath.
  • a known electroless plating bath can be used as the electroless plating bath.
  • the electroless plating bath is preferably an alkaline electroless plating bath (preferably having a pH of about 9 to 14) from the viewpoint of availability.
  • the substrate to which the electroless plating catalyst precursor is applied is immersed in the electroless plating bath, the substrate is washed with water to remove excess precursor (metal salt, etc.), and then in the electroless plating bath. Soak in. In this case, reduction of the plating catalyst precursor and subsequent electroless plating are performed in the electroless plating bath.
  • the electroless plating bath used here a known electroless plating bath can be used as described above.
  • the reduction of the electroless plating catalyst precursor may be performed as a separate step before electroless plating by preparing a catalyst activation liquid (reducing liquid) separately from the embodiment using the electroless plating liquid as described above.
  • the catalyst activation liquid is a liquid in which a reducing agent capable of reducing an electroless plating catalyst precursor (mainly metal ions) to zero-valent metal is dissolved, and the concentration of the reducing agent with respect to the whole liquid is 0.1 to 50% by mass. Preferably, 1 to 30% by mass is more preferable.
  • known reducing agents for example, boron-based reducing agents such as sodium borohydride or dimethylamine borane, formaldehyde, hypophosphorous acid, etc.
  • dipping keep the concentration of the electroless plating catalyst or its precursor near the surface of the layer to be plated in contact with the electroless plating catalyst or its precursor, and soak it with stirring or shaking. Is preferred.
  • composition of a general electroless plating bath for example, in addition to a solvent (for example, water), 1. 1. metal ions for plating; 2. reducing agent; Additives (stabilizers) that improve the stability of metal ions are mainly included.
  • the plating bath may contain known additives such as a plating bath stabilizer.
  • the organic solvent used in the plating bath needs to be a solvent that can be used in water, and from this point, ketones such as acetone and alcohols such as methanol, ethanol, and isopropanol are preferably used.
  • the types of metals used in the electroless plating bath for example, copper, tin, lead, nickel, gold, silver, palladium, rhodium are known, and from the viewpoint of conductivity, copper and gold are among others. Particularly preferred.
  • the optimal reducing agent and additive are selected according to the said metal.
  • the thickness of the metal layer obtained by electroless plating can be controlled by the metal ion concentration of the plating bath, the immersion time in the plating bath, or the temperature of the plating bath, but from the viewpoint of conductivity, it is 0. .1 ⁇ m or more is preferable, and 0.2 to 2 ⁇ m is more preferable. However, when performing electroplating to be described later using a metal layer formed by electroless plating as a conductive layer, it is preferable that a layer of at least 0.1 ⁇ m or more is uniformly applied.
  • the immersion time in the plating bath is preferably about 1 minute to 6 hours, and more preferably about 1 minute to 3 hours.
  • electrolytic plating electrolytic plating (electroplating)
  • the plating catalyst or its precursor applied in the above step has a function as an electrode
  • electrolytic plating can be performed on the layer to be plated to which the catalyst or its precursor is applied. it can.
  • the formed metal layer may be used as an electrode, and electrolytic plating may be further performed. Thereby, a new metal layer having an arbitrary thickness can be easily formed on the electroless plating layer having excellent adhesion to the substrate.
  • the metal layer can be formed in a thickness according to the purpose, which is suitable for applying the metal layer to various applications.
  • a conventionally known method can be used.
  • a metal used for electrolytic plating copper, chromium, lead, nickel, gold
  • the thickness of the metal layer obtained by electrolytic plating can be controlled by adjusting the concentration of metal contained in the plating bath, the current density, or the like.
  • the thickness of the metal layer is preferably 0.5 ⁇ m or more, more preferably 1 to 30 ⁇ m from the viewpoint of conductivity.
  • Pattern formation process is a process provided as needed, and is a process of etching the metal layer obtained by the plating process in pattern shape, and forming a pattern-shaped metal layer.
  • a metal layer having a desired pattern can be generated by removing unnecessary portions of the metal layer formed on the entire substrate surface by etching. More specifically, as shown in FIG. 1D, in this step, the patterned metal layer 18 is formed on the plated layer 12 by removing unnecessary portions of the metal layer.
  • any method can be used to form this pattern. Specifically, a generally known subtractive method (a patterned mask is provided on a metal layer, and an unformed region of the mask is etched). After that, the mask is removed to form a patterned metal layer), a semi-additive method (a plating process is performed so that a patterned mask is provided on the metal layer, and a metal layer is formed in a non-mask formation region) , Removing the mask, etching, and forming a patterned metal layer).
  • a generally known subtractive method a patterned mask is provided on a metal layer, and an unformed region of the mask is etched. After that, the mask is removed to form a patterned metal layer
  • a semi-additive method a plating process is performed so that a patterned mask is provided on the metal layer, and a metal layer is formed in a non-mask formation region
  • a resist layer is provided on the formed metal layer, the same pattern as the metal layer pattern portion is formed by pattern exposure and development, and the metal layer is removed with an etching solution using the resist pattern as a mask.
  • This is a method of forming a metal layer. Any material can be used as the resist, and negative, positive, liquid, and film-like ones can be used.
  • an etching method any method used at the time of manufacturing a printed wiring board can be used, and wet etching, dry etching, and the like can be used, and may be arbitrarily selected. In terms of operation, wet etching is preferable from the viewpoint of simplicity of the apparatus.
  • an etching solution for example, an aqueous solution of cupric chloride, ferric chloride, or the like can be used.
  • a resist layer is provided on the formed metal layer, the same pattern as the non-metal layer pattern portion is formed by pattern exposure and development, and the resist pattern is removed by electrolytic plating using the resist pattern as a mask.
  • This is a method of forming a patterned metal layer by performing quick etching later and removing the metal layer in a pattern.
  • the resist, the etching solution, etc. can use the same material as the subtractive method.
  • the above-described method can be used as the electrolytic plating method.
  • the layer to be plated may be removed together by a known means (for example, dry etching).
  • the laminate (surface metal layer material) obtained by the above production method has a metal layer as the outermost layer and can be used for various applications.
  • the present invention can be applied to various uses such as FPC, COF, TAB, motherboard, and package interposer substrate.
  • a known material can be used for the insulating layer, and examples thereof include a known interlayer insulating film and a solder resist.
  • the laminated body (metal pattern material) which has a pattern-like metal layer may be used as a board
  • the second embodiment of the laminate manufacturing method of the present invention includes a step (F) of forming an insulating layer on a substrate, a step (A ′) of forming a layer to be plated on the insulating layer, and a layer to be plated.
  • a step (D) of applying a precursor and a step (E) of performing a plating treatment are provided.
  • step (F) The main difference between the second embodiment and the first embodiment described above is the point of step (F).
  • this embodiment will be discussed with reference to FIG. 2 while mainly detailing the procedure (F).
  • FIG. 2 the same components as those shown in FIG. 1 are denoted by the same reference numerals, and the description thereof is omitted.
  • Step (F) is a step of forming an insulating layer on the surface of the substrate. By performing this step, insulation is further ensured. More specifically, in this step, the substrate 10 is prepared as shown in FIG. 2A, and the insulating layer 20 is formed on the surface as shown in FIG. First, materials (insulating layer etc.) used in this step will be described in detail, and then the procedure of this step will be described in detail.
  • thermosetting resin examples include epoxy resins, phenol resins, polyimide resins, polyester resins, bismaleimide resins, polyolefin resins, and isocyanate resins.
  • thermoplastic resin examples include phenoxy resin, polyether sulfone, polysulfone, polyphenylene sulfone, polyphenylene sulfide, polyphenyl ether, polyether imide, and the like.
  • the thickness of the insulating layer is appropriately selected depending on the purpose of use of the laminate, but is preferably 10 to 150 ⁇ m and more preferably 30 to 50 ⁇ m from the viewpoint of ensuring insulation.
  • the method for forming the insulating layer is not particularly limited.
  • an insulating resin composition containing an insulating resin is applied onto a substrate, and heat treatment or exposure treatment is performed as necessary to form an insulating layer (coating method) or an insulating resin is contained. And a method of laminating an insulating layer on the substrate.
  • a solvent may be included in the insulating resin composition.
  • a solvent having a boiling point which is not too high is preferable, and a solvent having a boiling point of about 40 to 150 ° C. is preferably selected.
  • cyclohexanone, methyl ethyl ketone, or the like can be used.
  • the concentration of the solid content in the insulating resin composition is preferably 2 to 50% by mass from the viewpoint of handleability.
  • step (F) step (A ′) of forming a layer to be plated on the obtained insulating layer is performed.
  • the procedure of the process is the same as the process (A) described above. By performing this step, the layer 12 to be plated is formed on the insulating layer 20 as shown in FIG.
  • step (C) described above is performed to convert the hydrophilicity / hydrophobicity of the layer to be plated.
  • step (D) is performed to give a plating catalyst or a precursor thereof to the layer to be plated.
  • the metal layer is formed on the layer to be plated by performing the subsequent step (E). More specifically, by carrying out this step, as shown in FIG. 2D, a metal layer 14 is provided on the layer 12 to be plated, and a laminate 16 is obtained.
  • the step (H) is performed to obtain a patterned metal layer. More specifically, as shown in FIG. 2E, in this step, the patterned metal layer 18 is formed on the plated layer 12 by removing unnecessary portions of the metal layer 14.
  • N, N-dimethylacetamide (16.2 g) was placed in a 500 mL three-necked flask and heated to 65 ° C. under a nitrogen stream. Thereto, N, N-dimethylacetamide (38 g) solution of monomer A (10.43 g) obtained above, t-butyl acrylate (12.67 g), V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) (0.24 g). was added dropwise over 4 hours. After completion of the dropwise addition, the reaction solution was further stirred for 3 hours. Thereafter, N, N-dimethylacetamide (154 g) was added to the reaction solution, and the reaction solution was cooled to room temperature.
  • the comparative polymer 1 does not contain a polarity converting group.
  • the comparative polymer 2 does not contain a specific crosslinkable group.
  • the comparative polymer 3 does not contain a polarity converting group or a specific crosslinkable group.
  • composition for forming plated layer A 30 wt% solution (3 g) of polymer A obtained above and propylene glycol monomethyl ether (hereinafter abbreviated as MFG) (7 g) were mixed and stirred to prepare a composition X for forming a layer to be plated.
  • MFG propylene glycol monomethyl ether
  • the prepared composition for plating layer X was applied on the insulating layer by spin coating so that the thickness of the layer to be plated was 1 ⁇ m, dried and cured at 150 ° C. for 30 minutes, and then the layer to be plated Formed.
  • the contact angle with respect to the water of the obtained to-be-plated layer was measured using the contact angle measuring apparatus (the Kyowa Interface Science company make, model: DM500), it was 89 degrees and was hydrophobic.
  • the remaining film ratio (%) from the film thickness before and after the alkali treatment ⁇ (thickness of the plated layer after the alkali treatment / thickness of the plated layer before the alkali treatment) ⁇ 100 ⁇ was measured.
  • the contact angle with respect to the water of a to-be-plated layer is measured using the contact angle measuring apparatus (the Kyowa Interface Science company make, model: DM500) after the said process (B)
  • a contact angle changes before and behind alkali treatment. It wasn't.
  • the substrate obtained in the step (C) was immersed in a 5 wt% aqueous solution (liquid temperature: 50 ° C.) of Sulcup ACL-009 (manufactured by Uemura Kogyo Co., Ltd.) for 5 minutes, and washed twice with pure water after immersion. Thereafter, the substrate subjected to the above treatment was immersed in an activator Neogant 834 (manufactured by Atotech Japan Co., Ltd.) which is a Pd catalyst application solution for 5 minutes at room temperature, and then washed twice with pure water after immersion.
  • an activator Neogant 834 manufactured by Atotech Japan Co., Ltd.
  • Step (E) Electroless plating
  • the substrate subjected to the above treatment was immersed in a reducer Neogant WA (manufactured by Atotech Japan), which is a Pd reducing agent, at 36 ° C. for 5 minutes and washed twice with pure water.
  • the palladium particle (electroless-plating catalyst) with an average particle diameter of 1 nm was provided to the to-be-plated layer by performing the said process.
  • the substrate was printed with Print Gantt PV (manufactured by Atotech Japan) (pH: 12.8, containing metal ions: copper ions, nickel ions, reducing agent: formaldehyde, amount of reducing agent: 0.45.
  • Print Gantt PV manufactured by Atotech Japan
  • a metal layer (plating layer) was prepared on the layer to be plated by immersing in mass% (relative to the total amount of liquid) at room temperature for 30 minutes.
  • the thickness of the obtained metal layer (electroless copper plating layer) was 0.5 ⁇ m.
  • Electroplating was performed on the obtained substrate with an electroless copper plating layer as follows.
  • As the electroplating solution use a mixed solution of water 1283g, copper sulfate pentahydrate 135g, 98% concentrated sulfuric acid 342g, 36% concentrated hydrochloric acid 0.25g, ET-901M (Rohm and Haas) 39.6g, and attach the holder
  • the substrate and the copper plate were connected to a power source, and electrolytic copper plating was performed at 3 A / dm 2 for 45 minutes to obtain a substrate having a metal layer of about 20 ⁇ m.
  • A a defect rate of 0% to less than 5%
  • B a defect rate of 5% to less than 10%
  • C a defect rate of 10% to less than 20%
  • D defect "E” with a rate of 20% or more: No plating was deposited
  • A Peel strength is 0.60 kN / m or more
  • B Peel strength is 0.30 kN / m or more and less than 0.60 kN / m
  • C Peel strength is 0.10 kN / m or more 0 “D” of less than 30 kN / m: No plating was deposited, and no metal layer was obtained.
  • Example 2 A laminate was produced according to the same procedure as in Example 1 except that a 30 wt% solution of polymer B was used instead of the 30 wt% solution of polymer A. The evaluation results are summarized in Table 1.
  • Example 3 A laminate was produced according to the same procedure as in Example 1 except that the polymer C was used instead of the polymer A, and the formation of the plated layer was changed to the following procedure.
  • the evaluation results are summarized in Table 1.
  • UVF-502S lamp: UXM-501MD
  • irradiation power 10 mW / cm 2 (ultraviolet integrated light meter UIT150 manufactured by Ushio Electric Co., Ltd.) -Irradiation power was measured with a light receiving sensor UVDS254) and cured for 500 seconds to form a layer to be plated.
  • Example 4 Instead of the composition X for forming the plating layer, a 30 wt% solution of polymer D (4 g), 1,4-butylene glycol diglycidyl ether (0.12 g) as a crosslinking agent, and MFG (6 g) were mixed and stirred. A laminate was produced according to the same procedure as in Example 1, except that the obtained composition for forming a layer to be plated was used. The evaluation results are summarized in Table 1.
  • Example 5 Instead of the composition X for forming the plating layer, a 30 wt% solution of polymer E (4 g), tolylene-2,4-diisocyanate (0.20 g) as a crosslinking agent, and MFG (6 g) were mixed and stirred. A laminate was produced according to the same procedure as in Example 1, except that the obtained composition for forming a layer to be plated was used. The evaluation results are summarized in Table 1.
  • Example 6 In place of the composition for forming a layer to be plated X, a layer to be plated formed by mixing and stirring a 30 wt% solution of polymer F (4 g), tetramethoxysilane (0.16 g) as a crosslinking agent, and MFG (6 g) A laminate was produced according to the same procedure as in Example 1 except that the composition for use was used. The evaluation results are summarized in Table 1.
  • Example 7 In place of the composition X for forming a layer to be plated, a 30 wt% solution of polymer G (4 g), 1,4-bis (chloromethyl) benzene (0.10 g) as a crosslinking agent, and MFG (6 g) were mixed and stirred. A laminate was produced according to the same procedure as in Example 1, except that the composition for forming a layer to be plated obtained was used. The evaluation results are summarized in Table 1.
  • Example 8> A laminate was produced according to the same procedure as in Example 1 except that a 30 wt% solution of polymer H was used instead of the 30 wt% solution of polymer A. The evaluation results are summarized in Table 1.
  • Example 9 A laminate was produced according to the same procedure as in Example 1 except that a 30 wt% solution of polymer I was used instead of the 30 wt% solution of polymer A. The evaluation results are summarized in Table 1.
  • Example 10> The same as Example 1 except that the polymer J was used instead of the polymer A, the formation of the layer to be plated was changed to the following procedure, and the following step (C1) was performed instead of the above step (C). A laminate was produced according to the procedure.
  • the evaluation results are summarized in Table 1.
  • Step (C1) The substrate obtained in the step (B) was baked at 150 ° C. for 30 minutes.
  • the IR spectrum of the plated layer after the heat treatment was measured using an ATR-infrared spectrophotometer, it was confirmed that the peak derived from the polar conversion group (acetal group) at 1141 cm ⁇ 1 had disappeared.
  • a peak derived from a carboxylic acid group was confirmed at 1710 cm ⁇ 1 . That is, it was confirmed that the polar conversion group was converted to a hydrophilic group (carboxylic acid group).
  • Example 11 According to the same procedure as in Example 1, except that the polymer K was used instead of the polymer A, the formation of the layer to be plated was changed to the following procedure, and the following step (C2) was performed instead of the step (C). A laminate was produced.
  • the evaluation results are summarized in Table 1.
  • the substrate obtained in the step (B) was heat baked at 150 ° C. for 30 minutes.
  • ATR- infrared spectrophotometer using was measured for IR spectrum of the plated layer after the heat treatment, the absorption of the sulfonic acid group was observed at 1030 cm -1 and 1000 cm -1. That is, it was confirmed that the polar conversion group was converted to a hydrophilic group (sulfonic acid group).
  • the contact angle of the layer to be plated after heat baking was 30 °, and it was confirmed that the layer to be plated was hydrophilized. From the above, it was confirmed that sulfonic acid groups were generated by heat baking, and the plated layer was made hydrophilic.
  • Example 12> The same as in Example 1 except that the polymer L was used instead of the polymer A, the formation of the layer to be plated was changed to the following procedure, and the following step (C3) was performed instead of the above step (C).
  • a multilayer substrate was manufactured according to the procedure.
  • Various measurement results are summarized in Table 1.
  • Step (C3) The substrate obtained in the step (B) was irradiated with 10 mW / cm 2 (USHIO ELECTRIC CO., LTD.) Using a 150 UV exposure machine (model number: manufactured by Mitsunaga Electric Co., Ltd. model number: UVF-502S, lamp: UXM-501MD). Exposure was carried out for 100 seconds using a UV integrated light meter UIT150 (irradiation power measurement by UVDS254, manufactured by Co., Ltd.). ATR- infrared spectrophotometer using was measured for IR spectrum of the plated layer after the heat treatment, the absorption of the sulfonic acid group was observed at 1030 cm -1 and 1000 cm -1.
  • the polar conversion group was converted to a hydrophilic group (sulfonic acid group).
  • the contact angle of the layer to be plated after exposure was 35 °, and it was confirmed that the layer to be plated was hydrophilized. From the above, it was confirmed that sulfonic acid groups were generated by exposure and the plated layer was made hydrophilic.
  • Example 13> A multilayer substrate was manufactured according to the same procedure as in Example 1 except that the formation of the layer to be plated was changed to the following procedure and the following step (C4) was performed instead of the above step (C). Various measurement results are summarized in Table 1.
  • Step (C4) Using a UV exposure machine (model number: manufactured by Mitsunaga Electric Co., Ltd. model number: UVF-502S, lamp: UXM-501MD), an irradiation power of 10 mW / cm 2 (made by Ushio Electric Co., Ltd.) The sample was exposed for 100 seconds with a UV integrated light meter UIT150-light receiving sensor UVDS254, and then heated at 90 ° C. for 5 minutes. When the IR spectrum of the layer to be plated after exposure and heat treatment was measured using an ATR-infrared spectrophotometer, it was confirmed that the peak derived from the polar conversion group (tertiary ester group) at 1367 cm ⁇ 1 disappeared.
  • a peak derived from a carboxylic acid group was newly confirmed at 1710 cm ⁇ 1 . That is, it was confirmed that the polar conversion group was converted to a hydrophilic group (carboxylic acid group).
  • the contact angle with respect to the water of the to-be-plated layer after the acid treatment by exposure was measured using a contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd., model: DM500), it was 48 °, and the contact angle of the to-be-plated layer was It was confirmed that it was decreasing.
  • the laminate produced using the composition for forming a layer to be plated according to the present invention has little plating unevenness and suppresses the contamination of the plating bath during plating. Moreover, the adhesiveness of the metal layer was also excellent. Furthermore, from the value of the water contact angle, it was confirmed that the to-be-plated layer formed using the composition for forming to-be-plated layer of this invention has changed from hydrophobic to hydrophilic by the polarity conversion process.
  • a specific crosslinkable group having high resistance to an alkaline aqueous solution is introduced, and when contacting with the alkaline aqueous solution, the polarity of the polarity conversion group in the plating layer is set to be hydrophobic, Increases the hydrophobicity of the plating layer and imparts resistance to an aqueous alkaline solution.
  • the polarity of the polarity conversion group is changed from hydrophobic to hydrophilic by a predetermined treatment, and the layer to be plated is made more hydrophilic, and the affinity for subsequent plating catalyst solution and plating solution is increased. Increase.
  • a laminate having a metal layer with little plating unevenness can be obtained while suppressing contamination of the plating solution.
  • the crosslinkable group is an epoxy group, oxetanyl group, hydroxyl group or alkoxysilyl group
  • the polarity converting group is a group represented by the general formula (1) or (2)
  • the adhesion of the metal layer is more excellent. It was confirmed.
  • Comparative Example 1 using Comparative Polymer 1 having no polarity conversion group the plating layer itself did not precipitate.
  • Comparative Example 2 using Comparative Polymer 2 (acryloyloxy group-containing polymer) having no predetermined crosslinkable group plating unevenness and plating bath contamination were poor.
  • Comparative Example 3 using Comparative Polymer 3 described in Patent Document 1 plating unevenness and plating bath contamination were poor.
  • Comparative Example 4 using Comparative Polymer 4 having no crosslinkable group plating unevenness and plating bath contamination were poor. Even when the same polymer A as in Example 1 was used, in Comparative Example 5 where the step (C) (polarity conversion step) was not performed, plating did not precipitate.
  • Example 14 The laminate having the metal layer obtained in Example 1 was heat-treated at 180 ° C./1 hour, and then a dry resist film (manufactured by Hitachi Chemical Co., Ltd .; RY3315, film) was formed on the surface of the laminate. 15 ⁇ m thick) was laminated at 70 ° C. and 0.2 MPa with a vacuum laminator (manufactured by Meiki Seisakusho: MVLP-600).
  • a glass mask capable of forming a comb-type wiring (compliant with JPCA-BU01-2007) as defined in JPCA-ET01 is closely attached to the laminate obtained by laminating the dry resist film, and the resist is adhered to 70 mJ with an exposure machine having a central wavelength of 405 nm. Irradiated with light energy. Development was performed by spraying a 1% Na 2 CO 3 aqueous solution onto the layered product after the exposure with a spray pressure of 0.2 MPa. Thereafter, the laminate was washed with water and dried to form a resist pattern for the subtractive method on the metal film.
  • Etching was performed by immersing the laminate on which the resist pattern was formed in an FeCl 3 / HCl aqueous solution (etching solution) at a temperature of 40 ° C., and the metal layer present in the region where the resist pattern was not formed was removed. Thereafter, the resist pattern is swollen and peeled off by spraying a 3% NaOH aqueous solution onto the laminate at a spray pressure of 0.2 MPa, neutralized with a 10% sulfuric acid aqueous solution, and washed with water to form a comb-shaped wiring (pattern A metal film was obtained.
  • a solder resist (PFR800; manufactured by Taiyo Ink Mfg. Co., Ltd.) is vacuum-laminated on a laminate having a patterned copper metal layer under conditions of 110 ° C. and 0.2 MPa, and an exposure machine having a center wavelength of 365 nm. The light energy of 420 mJ was irradiated.
  • the laminate was subjected to a heat treatment at 80 ° C./10 minutes, and then developed by applying a NaHCO 3 : 10% aqueous solution to the laminate surface at a spray pressure of 2 kg / m 2 and dried. Thereafter, the laminate was irradiated again with light energy of 1000 mJ with an exposure machine having a center wavelength of 365 nm. Finally, a heat treatment at 150 ° C./1 hr was performed to obtain a wiring board coated with a solder resist.
  • Substrate 12 Plated layer 14: Metal layer 16: Laminate 18: Patterned metal layer 20: Insulating layer

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PCT/JP2012/065849 2011-07-29 2012-06-21 被めっき層形成用組成物、および金属層を有する積層体の製造方法 WO2013018454A1 (ja)

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US20150125674A1 (en) * 2013-11-05 2015-05-07 Thomas B. Brust Forming conductive metal patterns using reactive polymers
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KR102463945B1 (ko) * 2017-02-14 2022-11-04 닛산 가가쿠 가부시키가이샤 배선 형성 방법
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